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The structure of the title compound, [V(C5H5)2Cl(C2H3N)][FeCl4], a potential spermicidally active species, has been determined. This compound has a typical bent metallocene structure, in which two η5-bonded cyclo­penta­dienyl rings, an N-coordinated acetonitrile molecule and a Cl ligand occupy tetrahedral positions around the VIV atom. The V—N bond length was found to be 2.087 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804032830/ww6317sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536804032830/ww6317Isup2.hkl
Contains datablock I

CCDC reference: 262272

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.022
  • wR factor = 0.054
  • Data-to-parameter ratio = 21.3

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) V1 - N1 .. 5.32 su
Author Response: : The anisotropic displacement parameters of nitrogen in acetonitrile moiety are affected by large deviations of its electron density from approximation of independent atom model due delocalization into multiple bonds system. Therefore the refinement of parameters of either anharmonic thermal motion or atom asphericity would probably solve the problem, however it is behind the scope of this experiment.
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Fe1
Author Response: : Probably false alarm as Fe is in the centre of gravity of isolated FeCl4 moiety, serving as pivot atom for the most displacements.

Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.49 From the CIF: _reflns_number_total 3946 Count of symmetry unique reflns 2269 Completeness (_total/calc) 173.91% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1677 Fraction of Friedel pairs measured 0.739 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Acetonitrilechlorobis(η5-cyclopentadienyl)vanadium(IV) tetrachloroiron(III) top
Crystal data top
[V(C5H5)2Cl(C2H3N)][FeCl4]F(000) = 904
Mr = 455.27Dx = 1.756 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 27318 reflections
a = 7.3730 (2) Åθ = 1–27.5°
b = 13.5290 (3) ŵ = 2.15 mm1
c = 17.2680 (3) ÅT = 150 K
V = 1722.47 (7) Å3Plate, green
Z = 40.5 × 0.42 × 0.18 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
3946 independent reflections
Radiation source: fine-focus sealed tube3789 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 1.9°
φ and ω scans to fill the Ewald sphereh = 99
Absorption correction: integration
Gaussian (Coppens & Hamilton, 1970)
k = 1717
Tmin = 0.405, Tmax = 0.712l = 2222
26509 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.054 w = 1/[σ2(Fo2) + (0.0261P)2 + 0.6271P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
3946 reflectionsΔρmax = 0.29 e Å3
185 parametersΔρmin = 0.38 e Å3
0 restraintsAbsolute structure: Flack (1983), with how many Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.003 (13)
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
V10.63054 (4)0.95681 (2)0.552522 (17)0.01552 (7)
C10.9281 (3)0.90703 (15)0.53904 (12)0.0253 (4)
H10.98570.86540.57420.030*
C20.8295 (3)0.87676 (17)0.47408 (12)0.0262 (4)
H20.80660.81180.45950.031*
C30.7713 (3)0.9618 (2)0.43487 (12)0.0360 (5)
H30.70560.96310.38890.043*
C40.8291 (3)1.04389 (17)0.47678 (15)0.0386 (6)
H40.80791.10960.46390.046*
C50.9257 (3)1.00999 (16)0.54230 (14)0.0328 (5)
H50.97811.04910.58050.039*
C60.5342 (3)1.00632 (15)0.67307 (12)0.0278 (5)
H60.55880.97010.71760.033*
C70.3831 (3)0.99371 (16)0.62469 (12)0.0286 (4)
H70.29190.94680.63080.034*
C80.3939 (3)1.06489 (16)0.56501 (12)0.0305 (4)
H80.31041.07390.52530.037*
C90.5520 (3)1.11912 (15)0.57638 (13)0.0304 (5)
H90.59231.17090.54540.037*
C100.6416 (3)1.08242 (15)0.64301 (12)0.0283 (4)
H100.75131.10470.66300.034*
N10.6402 (2)0.82581 (12)0.61624 (9)0.0228 (3)
C110.6483 (3)0.75386 (15)0.65019 (11)0.0246 (4)
C120.6593 (3)0.66295 (17)0.69448 (14)0.0336 (5)
H12D0.59470.67070.74240.057 (18)*0.50
H12E0.78410.64800.70510.024 (12)*0.50
H12F0.60630.60990.66520.045 (15)*0.50
H12A0.75600.62280.67460.067*0.50
H12B0.54670.62770.69020.067*0.50
H12C0.68230.67820.74790.067*0.50
Cl10.40993 (8)0.87440 (4)0.47654 (3)0.03139 (12)
Fe10.11245 (4)0.83620 (2)0.798789 (15)0.02197 (7)
Cl20.16516 (8)0.74293 (4)0.69784 (3)0.03340 (12)
Cl30.01846 (8)0.97165 (4)0.75778 (3)0.03372 (13)
Cl40.06343 (10)0.75477 (4)0.87977 (4)0.04391 (16)
Cl50.36852 (11)0.87179 (5)0.85517 (4)0.05383 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.01477 (14)0.01510 (13)0.01669 (14)0.00005 (12)0.00139 (12)0.00017 (11)
C10.0146 (9)0.0327 (10)0.0285 (10)0.0049 (8)0.0037 (8)0.0047 (8)
C20.0230 (10)0.0305 (11)0.0250 (10)0.0038 (8)0.0085 (8)0.0065 (8)
C30.0267 (11)0.0595 (15)0.0217 (10)0.0093 (11)0.0086 (8)0.0127 (10)
C40.0307 (12)0.0271 (11)0.0578 (15)0.0064 (9)0.0273 (11)0.0164 (10)
C50.0173 (10)0.0352 (11)0.0459 (13)0.0077 (8)0.0087 (9)0.0097 (10)
C60.0354 (12)0.0285 (11)0.0194 (9)0.0051 (9)0.0067 (8)0.0036 (8)
C70.0199 (10)0.0320 (11)0.0341 (11)0.0009 (9)0.0100 (9)0.0063 (8)
C80.0247 (10)0.0324 (11)0.0343 (11)0.0151 (9)0.0005 (9)0.0037 (9)
C90.0397 (13)0.0170 (9)0.0347 (11)0.0054 (9)0.0088 (9)0.0012 (8)
C100.0283 (11)0.0263 (10)0.0302 (10)0.0002 (9)0.0024 (9)0.0131 (8)
N10.0245 (9)0.0218 (8)0.0221 (7)0.0009 (7)0.0037 (7)0.0022 (6)
C110.0224 (10)0.0269 (10)0.0244 (9)0.0006 (8)0.0022 (8)0.0012 (8)
C120.0361 (12)0.0278 (11)0.0369 (11)0.0007 (10)0.0031 (10)0.0138 (10)
Cl10.0301 (3)0.0320 (3)0.0321 (3)0.0069 (2)0.0083 (2)0.0054 (2)
Fe10.02673 (15)0.02026 (13)0.01892 (13)0.00017 (12)0.00264 (11)0.00072 (10)
Cl20.0450 (3)0.0294 (3)0.0258 (2)0.0052 (2)0.0044 (2)0.0062 (2)
Cl30.0427 (3)0.0287 (3)0.0297 (3)0.0115 (2)0.0006 (2)0.0018 (2)
Cl40.0588 (4)0.0317 (3)0.0412 (3)0.0015 (3)0.0238 (3)0.0056 (2)
Cl50.0522 (4)0.0472 (4)0.0620 (4)0.0133 (3)0.0364 (4)0.0083 (3)
Geometric parameters (Å, º) top
Cg1—V11.956 (1)C5—H50.9300
Cg2—V11.958 (1)C6—C101.399 (3)
V1—N12.0873 (16)C6—C71.403 (3)
V1—C72.265 (2)C6—H60.9300
V1—C22.272 (2)C7—C81.413 (3)
V1—C32.283 (2)C7—H70.9300
V1—C82.286 (2)C8—C91.391 (3)
V1—C42.290 (2)C8—H80.9300
V1—C62.2991 (19)C9—C101.417 (3)
V1—C52.299 (2)C9—H90.9300
V1—C12.3070 (19)C10—H100.9300
V1—C92.308 (2)N1—C111.138 (3)
V1—C102.3101 (19)C11—C121.451 (3)
V1—Cl12.3685 (6)C12—H12D0.9600
C1—C51.394 (3)C12—H12E0.9600
C1—C21.398 (3)C12—H12F0.9600
C1—H10.9300C12—H12A0.9600
C2—C31.402 (3)C12—H12B0.9600
C2—H20.9300C12—H12C0.9600
C3—C41.392 (4)Fe1—Cl52.1781 (7)
C3—H30.9300Fe1—Cl22.1867 (6)
C4—C51.413 (4)Fe1—Cl32.1889 (6)
C4—H40.9300Fe1—Cl42.2025 (6)
Cg1—V1—Cg2134.10 (4)V1—C1—H1123.0
N1—V1—C785.68 (7)C1—C2—C3107.8 (2)
N1—V1—C283.54 (7)C1—C2—V173.61 (11)
C7—V1—C2162.43 (8)C3—C2—V172.49 (12)
N1—V1—C3118.61 (8)C1—C2—H2126.1
C7—V1—C3148.15 (8)C3—C2—H2126.1
C2—V1—C335.86 (8)V1—C2—H2119.7
N1—V1—C8121.29 (8)C4—C3—C2108.0 (2)
C7—V1—C836.16 (8)C4—C3—V172.55 (12)
C2—V1—C8148.64 (8)C2—C3—V171.64 (11)
C3—V1—C8114.33 (8)C4—C3—H3126.0
N1—V1—C4135.74 (8)C2—C3—H3126.0
C7—V1—C4135.72 (8)V1—C3—H3121.6
C2—V1—C459.45 (8)C3—C4—C5108.15 (19)
C3—V1—C435.46 (10)C3—C4—V171.99 (12)
C8—V1—C4102.28 (8)C5—C4—V172.43 (12)
N1—V1—C677.33 (7)C3—C4—H4125.9
C7—V1—C635.80 (8)C5—C4—H4125.9
C2—V1—C6151.44 (8)V1—C4—H4121.4
C3—V1—C6159.67 (9)C1—C5—C4107.3 (2)
C8—V1—C659.51 (8)C1—C5—V172.69 (12)
C4—V1—C6124.39 (9)C4—C5—V171.69 (12)
N1—V1—C5105.89 (8)C1—C5—H5126.3
C7—V1—C5137.37 (8)C4—C5—H5126.3
C2—V1—C559.47 (8)V1—C5—H5121.1
C3—V1—C559.46 (9)C10—C6—C7108.56 (19)
C8—V1—C5121.96 (8)C10—C6—V172.76 (11)
C4—V1—C535.88 (9)C7—C6—V170.79 (11)
C6—V1—C5105.71 (8)C10—C6—H6125.7
N1—V1—C176.87 (7)C7—C6—H6125.7
C7—V1—C1152.37 (8)V1—C6—H6122.4
C2—V1—C135.55 (8)C6—C7—C8107.8 (2)
C3—V1—C159.09 (8)C6—C7—V173.41 (12)
C8—V1—C1157.20 (8)C8—C7—V172.74 (12)
C4—V1—C158.96 (8)C6—C7—H7126.1
C6—V1—C1118.05 (8)C8—C7—H7126.1
C5—V1—C135.24 (7)V1—C7—H7119.6
N1—V1—C9136.25 (7)C9—C8—C7107.7 (2)
C7—V1—C959.34 (8)C9—C8—V173.22 (12)
C2—V1—C9136.22 (8)C7—C8—V171.11 (12)
C3—V1—C9104.17 (9)C9—C8—H8126.1
C8—V1—C935.25 (8)C7—C8—H8126.1
C4—V1—C976.87 (8)V1—C8—H8121.3
C6—V1—C958.91 (8)C8—C9—C10108.70 (19)
C5—V1—C987.32 (8)C8—C9—V171.53 (11)
C1—V1—C9122.30 (8)C10—C9—V172.22 (12)
N1—V1—C10105.48 (7)C8—C9—H9125.7
C7—V1—C1059.62 (8)C10—C9—H9125.7
C2—V1—C10136.99 (8)V1—C9—H9122.3
C3—V1—C10124.35 (9)C6—C10—C9107.2 (2)
C8—V1—C1059.52 (8)C6—C10—V171.91 (11)
C4—V1—C1089.15 (9)C9—C10—V172.06 (11)
C6—V1—C1035.33 (8)C6—C10—H10126.4
C5—V1—C1077.77 (8)C9—C10—H10126.4
C1—V1—C10104.44 (8)V1—C10—H10121.4
C9—V1—C1035.72 (8)C11—N1—V1178.70 (17)
N1—V1—Cl185.17 (5)N1—C11—C12179.2 (2)
C7—V1—Cl181.68 (6)C11—C12—H12D109.5
C2—V1—Cl183.62 (6)C11—C12—H12E109.5
C3—V1—Cl180.40 (7)C11—C12—H12F109.5
C8—V1—Cl180.17 (6)C11—C12—H12A109.5
C4—V1—Cl1111.40 (7)C11—C12—H12B109.5
C6—V1—Cl1115.25 (6)H12A—C12—H12B109.5
C5—V1—Cl1139.02 (6)C11—C12—H12C109.5
C1—V1—Cl1117.38 (6)H12A—C12—H12C109.5
C9—V1—Cl1111.99 (6)H12B—C12—H12C109.5
C10—V1—Cl1138.18 (6)Cl5—Fe1—Cl2109.26 (3)
C5—C1—C2108.6 (2)Cl5—Fe1—Cl3109.98 (3)
C5—C1—V172.07 (12)Cl2—Fe1—Cl3107.67 (2)
C2—C1—V170.84 (11)Cl5—Fe1—Cl4109.70 (3)
C5—C1—H1125.7Cl2—Fe1—Cl4108.79 (2)
C2—C1—H1125.7Cl3—Fe1—Cl4111.38 (3)
Selected geometric parameters (Å, °). top
Cg1—V11.956 (1)Cg1—V1—Cg2134.10 (4)
Cg2—V11.958 (1)Cl1—V1—N185.17 (4)
V1—N12.087 (2)N1—C111.138 (3)
V1—Cl12.369 (1)C11—C121.451 (3)
V1—N1—C11178.7 (2)
Cg1 is the centroid of atoms C1–C5 and Cg2 is the centroid of atoms C6–C10
 

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